Detergent composition



United States Patent 3,338,838 DETERGENT COMPOSITION Eugene Royce Wilson, Wyoming, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Nov. 17, 1964, Ser. No. 411,713 6 Claims. (Cl. 252-161) This invention relates to detergent compositions having superior properties with respect to mildness, detergency and sudsing. Specifically, this invention relates to built detergent compositions containing salts of esters of alpha sulfonated fatty acids.

Soluble salts, e.g., sodium or potassium salts, of methyl or ethyl esters of alpha-sulfonated fatty acids have been known as detergent materials. Heretofore, however, the use of these materials in built detergent compositions for laundry and dishwashing purposes has been attended by various problems relating to detergency and sudsing. It has now been discovered that by combining these materials with other detergent materials hereinafter described in detail, many of the problems attendant to the use of said salts of esters of alpha-sulfonated fatty acids can be avoided.

Accordingly, it is an object of this invention to provi-de detergent compositions having superior mildness and desirable detergency properties.

It is a further object of this invention to provide detergent compositions, utilizing mild detergent materials, which have desirable sudsing properties.

It is a further and more specific object of this invention to provide such detergent compositions which are economical to prepare.

These objects and others can be achieved with a built detergent composition consisting essentially of (A) from about 80% to about 10% of an organic detergent mixture consisting essentially of (1) from about 20% to about 80% of an alkali metal salt of the ester of a short chain monohydric alcohol containing from 1 to about 2 carbon atoms and alpha-sulfonated fatty acids containing from about 10 to about 20 carbon atoms; (2) from 0% to about 80% of an alkali metal salt of an alkyl sulfate wherein said alkyl radical contains from about 14 to about 20 carbons and (3) from 0% to about 80% of a dialkalimetal-salt of an alpha-sulfonated fatty acid containing from about 14 to about 20 carbon atoms and (B) from about 20% to about 90% of water soluble alkaline detergency builder salt. The preferred alkali metal salts are the sodium and potassium salts.

There are several preferred combinations of organic detergent ingredients within the scope of the invention hereinbefore defined. For example, the alkali metal salt of the lower alkyl ester of an alpha-sulfonated fatty acid, hereinafter referred to as ASCA, Which is derived from either methyl or ethyl alcohol and fatty acids derived from coconut oil, i.e., ethyl or methyl coconut ASCA, forms a synergistic combination with alkali metal tallow alkyl sulfate, e.g., derived from tallow fatty alcohols, hereinafter referred to as TAS. Tallow and coconut are hereinafter more fully defined. When methyl or ethyl coconut ASCA and TAS are combined in the ratio of I from about 2:1 to about 1:4, the amount of suds formed by the mixture is synergistically greater than the amount of suds formed by either organic detergent alone. The preferred combination of 3:1 TAS/ethyl (or methyl) coconut ASCA gives a suds performance almost twice what an equal amount by weight of either component alone will give. Such mixtures of detergents are very mild to the skin and exhibit excellent heavy duty detergency when used in the compositions of this invention.

Another preferred combination is the combination of methyl or ethyl tallow ASCA (based on tallow fatty acids) and dial-kalimetal-salts of alpha-sulfonated fatty acids derived from tallow, hereinafter referred to as tallow ASC. Combinations of these two detergents in ratios of from about 3:1 to about 1:3 tallow ASC to methyl or ethyl tallow ASCA give detergency superior to compositions containing equal weights of either organic detergent alone. There also appears to be a type of sudsing synergism in mixtures of these two detergents since the sudsing performance of mixtures is greater than would have been predicted if a straight line sudsing relationship had existed. The preferred ratio of tallow ASC to ethyl or methyl tallow ASCA is 3:2.

Another preferred combination of organic detergents involves mixtures of ASCAs derived from coconut and tallow fatty acids. Mixtures of the tallow and coconut ASCA have superior sudsing characteristics to either organic detergent alone. Ratios from about 3:1 to about 1:3, tallow:coconut display this synergistic interaction.

One other preferred combination of organic detergents is the ternary combination of from about 15% to about ethyl or methyl coconut ASCA; from about 10% to about 65% tallow ASC; and from about 5% to about 45% of ethyl or methyl tallow ASCA, percentages being based on the total combination. This combination is an optimum, taking into account sudsing and detergency in both hard and soft waters.

The ASCA of this invention is normally derived from methyl or ethyl alcohols which are approximately equivalent insofar as performance considerations are concerned. Normally the methyl ASCA derivatives are preferred from the standpoint of cost considerations. The fatty acids which are used to prepare the ASCA of this invention are normally derived from suitable naturally occurring mixtures such as those fatty acids derived from coconut oil and tallow. However, snythetically prepared fatty acids having chain lengths within the limits previously described are suitable, especially those which generally correspond to coconut and tallow fatty acids. The source of the fatty acids is not critica The alkali metal salts such as the sodium salts, of alkyl sulfates hereinbefore described are also normally derived from mixtures of alcohols such as those prepared by bydrogenating the fatty acids derived from naturally occurring glycerides such as tallow. Synthetically produced compounds containing alkyl groups, such as those derived from petroleum hydrocarbons, are also suitable so long as the alkyl groups are chemically similar to those derived from tallow.

The source of the fatty acids for preparation of tallow ASC can be essentially the same as for the preparation of the tallow ASCA.

It is understood that when, herein, coconut is used, unqua-lifiedly, it refers to acyl and alkyl groups such as those derived from coconut or similar oil, i.e., those rich in, or substantially completely comprising, fatty acyl groups containing about 12 carbon atoms, e.g., the acyl group in lauric acid. Similarly, the term tallow as used herein refers to acyl and alkyl groups such as those derived from tallow, i.e., those rich in fatty acyl or alkyl groups containing 16 and 18 carbon atoms, e.g., cetyl and stearyl alkyl groups and palmitoyl and stearoyl acyl groups. Both the tallow and coconut groups can be derived from either natural or synthetic raw materials.

The compositions of this invention contain from about 20% to about of Water soluble alkaline detergency builder salts, either of the organic or inorganic types, and should provide a Washing solution pH of about 9 to about 12. The ratio of builder salts to organic detergent is pref erably from about 0.7 :1 to about 9:1. Examples of water soluble inorganic alkaline detergency builder salts are alkali metal carbonates, phosphates, polyphosphates, and silicates. Specific examples of such salts are sodium and potassium tripolyphosphates, carbonates, pyrophosphates, orthophos'phates, and hexametaphosphates. Examples of organic alkaline detergency builder salts are (1) alkali metal amino polycarboxylates [e.g., sodium and potassium ethylenediaminetetraacetates, N-(2-hydroxyethyl)-ethylenediaminetriacetates, nitrilo triacetates, and N-(Z-hydroxyethyl)-nitrolo diacetates]; (2) alkali metal salts of phytic acid (e.g., sodium and potassium phytatessee US. Patent 2,739,942); (3) Water soluble salts of ethanel-hydr-oxy-1,1-diphosphate (e.g., the trisodium and tripotassium salts); (4) water soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in the Diehls US. Patent 3,213,030 issued Oct. 19, 1965); (5) water soluble salts of substituted methylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphones disclosed in the 'copending application of Clarence H. Roy, Ser. No. 266,055, filed Mar. 18, 1963); (6) Water soluble salts of polycarboxylate polymers and copolymers as described in the copending application of Francis L. Diehl, Ser'. No. 269,359, filed Apr. 1, 1963 (e.g., polymers of itaconic acid, aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene malonic acid; and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene); and (7) mixtures thereof.

Mixtures of organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate, and trisodium ethane-1- hydroxy-l,l-diphosphonate.

Those builders which are the more effective calcium ion sequestrants are preferred since ASCA is more susceptible to being affected by water hardness than many synthetic detergents. The effective builders such as tripolyphosphates and especially the organic sequestrants in amounts sufficient to effectively sequester the, e.g., cal cium ions in the water make the compositions of this invention especially efiective.

The compositions of this invention can also contain from about .5 to about 5%, preferably 5%, of an organic suds builder selected from the group consisting of C -C fatty alcohols, normal amides, short chain, i.e., 1 to about 3 carbon atoms, N-alkyl amides, short chain, i.e., 1 to about 3 carbon atoms, alkanol and dialkanol amides of C -C fatty acids. The fatty alcohols such as dodecanol, tetradecano-l or hexadecanol are the preferred suds builders for the ASCAs of this invention. However, there are preferred suds building advantages in mixtures of C -C fatty alcohols and monoethanol amides derived from coconut fatty acids in the ratio of 3:1 fatty alcohol to amide. This combination of organic suds builders also can be advantageously used in ratios within the range of 3:1 to 1:1 alcohol to amide. The ratio of organic detergent to organic suds builder can be varied from about 7:1 to about 1.421 with essentially the same performance. Accordingly, lower levels or organic suds builders are preferred for formulation ease.

Other minor ingredients can also be added if desired, but are not essential, to the detergent compositions which are prepared using the organic detergent combinations of this invention. Such ingredients include soil suspending SUDS WHEEL This test involved measuring the suds heights obtained after a standard agitation of aqueous solutions having concentrations of detergent compositions of 0.1%, 0.2%, 0.3%, 0.4% and 0.5%. These solutions were prepared by adding the detergent compositions to water containing a standard quantity of a standard artificial soil. The value given is the aver-age of the five measured suds heights divided by the average height found when the same test invention were tested using the is run with a standard composition as hereinafter defined.

THE MINIATURE WASHER A small washing machine, having a capacity of eight liters of washing solution was loaded with artificially soiled cotton cloths, which were then washed following agents, such as alkali metal and ammonium salts of cara standardized procedure. The artificial soil had a high oil content. Suds height was measured and expressed as a fraction of the suds height given by the standard composition in the same test. Detergency of the laundered cloth was then measured, in terms of whitening effect as measured by a photovolt meter when compared with the whitening effect achieved with a standard composition used with the same procedure in the same machine. The concentration used was 0.35% of the complete composition by weight of the solution.

STANDARD COMPOSITION The standard composition, with which the compositions of this invention were compared, had the following formula. This is a high sudsing composition, but somewhat lacking in mildness and having average laundering detergency.

Percent Sodium salt of sulfated coconut oil fatty alcohol 17.5 Sodium tripolyphosphate (hereinafter referred to as STP) 52.0

AMPLES The general formula of the compositions of this invention which were tested was as follows:

Percent Organic detergent 17.5 STP 52.0 Sodium sulfate 17.5 Silicate (31% solids) (1.6:1; SiO :Na O) 6.0 Suds booster 5.0 Moisture Balance Tallow in the several tallow-based compounds in the following examples had the following chain length distribution: 3.5% C 31% C 65.5% C and the coconut had the following chain length distribution: .7% C

8.9% C 6.8% C 47.2% C 18.6% C 8.3% C and 9.5% C

Example I HESS.

TAS, Laurie ASCA, Sudsing Percent Percent Performance There is a clear case of a synergistic interaction between the TAS and lauric ASCA with respect to sudsing within the ratios of TASzlauric ASCA of 4:1 to 1:2'. The compositions of this invention exemplified in this example are much milder than the standard composition and have excellent heavy-duty laundering detergency.

For comparison purposes, a similar series in which the sodium salt of a coconut alkyl sulfuric acid, (CNAS) is substituted for the TAS gave the following results when sudsing characteristics were determined in the same way.

CNAS, LauricASCA, Sudsing Percent Percent Performance There was essentially no sudsing synergism evidenced in these compositions. Also, these compositions containing CNAS were not as mild or as effective cleaning agents as the corresponding compositions containing TAS.

Example II Tallow ASC, Tallow ASCA, Detergency Percent Percent Performance In this series, a clear example of detergency synergism is shown. These compositions are exceptionally mild.

Example III The next series of miniature washer tests compared sodium salts of ethyl esters of a-sulfonated fatty acids (tallow and lauric). The compositions have the same formulation as in Example I with the exception of the active organic detergent which is set forth in the following table. The same solution conditions as those given in the washing performance of Example II were used.

Tallow ASCA, Coconut ASCA, Sudsing Percent Percent Performance Again, this is a clear example of sudsing synergism. These compositions were much milder than the standard composition.

Example IV In the following series of miniature washer tests, the organic detergent was about 25% sodium salt of the ethyl ester of wsulfonated fatty acids derived from coconut oil; about 56.25% disodium salt of ot-sulfonated fatty acids derived from tallow and about 18.75% of the sodium salt of the ethyl ester of a a-sulfonated tallow fatty acids. The total of the amounts of middle cut coconut alcohols and monoethanol amides of coconut fatty acids was held at 5% and the amounts of each suds booster were varied as follows. (The solution conditions were pH 10, 140 F. temperature, and 7 grains hardness.

Alcohol, Amide, Sudsing Percent Percent Performance In the following suds wheel tests, the organic detergent was either (1) a mixture T of a 1:1 mixture of disodium salts of a-sulfonated fatty acids derived from tallow and sodium salts of the ethyl esters of a-sul-fonated fatty acids derived from tallow, (2) sodium salts of the ethyl esters of a-sulfonated fatty acids derived from middle-cut coconut oil L and (3) mixtures thereof as set forth in the following table. The conditions were F. water having a pH of 10 and hardness of 21 grains. The suds booster for this example was 3.75% of middle-cut coconut alcohol.

'1, Percent L, Percent Sudsiug Performance enediaminetetraacetates; N-(Z-hydroxyethyl)-ethylenediaminetriacetates; nitrilotriacetates; N-(2-hydroxyethyl)- nitrilo triacetates; phytates; ethane-1-hydroxy-1,1-diphosphonates; methylene diphosphonates; ethylidene diphosphonate; isopropylidene diphosphonates; benzylmethylidene diphosphonates; and salts of polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, citraconic acid with themselves and monomers such as ethylene; and mixtures there of are substituted either wholly or in part for the sodium tripolyphosphate and/ or sodium silicate in the above examples, essentially equivalent results are obtained in that the sudsing and detergency synergisms are still present with respect to the organic detergents.

What is claimed is:

1. A built detergent composition consisting essentially of (A) from about 80% to about of an organic detergent mixture consisting essentially of (1) an alkali metal salt of the ester of a short chain monohydric alcohol selected from the group consisting of methyl and ethyl alcohols, and alpha-sulfonated coconut fatty acids and (2) an alkali metal tallow alkyl sulfate, the ratio of detergent (1) to detergent (2) being from about 2:1 to about 1:4 and (B) from about 20% to about 90% of Water soluble alkaline detergency builder salt.

2. A built detergent composition consisting essentially of (A) from about 80% to about 10% of an organic detergent mixture consisting essentially of (1) an alkali metal salt of the ester of an alcohol selected from the group consisting of methyl and ethyl alcohols and alpha sulfonated tallow fatty acids and (2) dialkali metal salts of alpha-sulfonated tallow fatty acids, the ratio of detergent (1) to detergent (2) being from about 3:1 to about 1:3 and (B) from about 20% to about 90% of water soluble alkaline detergency builder salt.

3. A built detergent composition consisting essentially of (A) from about 80% to about 10% of an organic detergent mixture consisting essentially of (1) from about 15% to about of alkali metal salts of esters of an alcohol selected from the group consisting of ethyl and methyl alcohols and alpha-sulfonated coconut fatty acids, (2) from about 10% to about 65% of the dialkalimetal-salt of alpha-sulfonated tallow fatty acids, and (3) from about 5% to about 45% of alkali metal salts of esters of an alcohol selected from the group consisting of methyl and ethyl alcohols and alpha-sulfonated tallow fatty acids, the percentages being by weight of the combination of organic detergents and (B) from about 20% to about of Water soluble alkaline detergency builder salt.

4. The composition of claim 1 wherein the ratio of detergent (1) to detergent (2) is about 1:3.

5. The detergent composition of claim 2, wherein the ratio of detergent (1) to detergent (2) is about 2:3.

6. The detergent composition of claim 1 wherein said water-soluble alkaline detergency builder salt is sodium tripolyphosphate.

References Cited UNITED STATES PATENTS 2,867,586 1/1959 Weil et a1 252l52 2,915,473 12/1959 Stirton 252-121 X 3,219,584 11/1965 Stirton 252-121 X 3,247,121 4/1966 Hendricks 252-121 X FOREIGN PATENTS 1,363,269 5/1964 France.

OTHER REFERENCES Surface Active Agents, Schwartz et al., Interscience r PubL, 1949, page 85.

LEON D. ROSDOL, Primary Examiner.

S. E. ,DARDEN, Assistant Examiner. 

1. A BUILT DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF (A) FROM ABOUT 80% TO ABOUT 10% OF AN ORGANIC DETERGENT MIXTURE CONSISTING ESSENTIALLY OF (1) AN ALKALI METAL SALT OF THE ESTER OF A SHORT CHAIN MONOHYDRIC ALCOHOL SELECTED FROM THE GROUP CONSISTING OF METHYL AND ETHYL ALCOHOLS, AND ALPHA-SULFONATED COCONUT FATTY ACIDS AND (2) AN ALKALI METAL TALLOW ALKYL SULFATE, THE RATIO OF DETERGENT (1) TO DETERGENT (2) BEING FROM ABOUT 2:1 TO ABOUT 1:4 AND (B) FROM ABOUT 20* TO ABOUT 90% OF WATER SOLUBLE ALKALINE DETERGENCY BUILDER SALT.
 3. A BUILT DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF (A) FROM ABOUT 80% TO ABOUT 10% OF AN ORGANIC DETERGENT MIXTURE CONSISTING ESSENTIALLY OF (1) FROM ABOUT 15% TO ABOUT 75% OF ALKALI METAL SALTS OF ESTERS OF AN ALCOHOL SELECTED FROM THE GROUP OF ETHYL AND METHYL ALCOHOLS AND ALPHA-SULFONATED COCONUT FATTY ACIDS, (2) FROM ABOUT 10% TO ABOUT 65% OF THE DIALKALIMETAL-SALT OF ALPHA-SULFONATED TALLOW FATTY ACIDS, AND (3) FROM ABOUT 5% TO ABOUT 45% OF ALKALI METAL SALTS OF ESTERS OF AN ALCOHOL SELECTED FROM THE GROUP CONSISTING OF METHYL AND ETHYL ALCOHOLS AND ALPHA-SULFONATED TALLOW FATTY ACIDS, THE PERCENTAGES BEING BY WEIGHT OF THE COMBINATION OF ORGANIC DETERGENTS AND (B) FROM ABOUT 20% TO ABOUT 90% OF WATER SOLUBLE ALKALINE DETERGENCY BUILDER SALT. 